Method of upgrading heavy hydrocarbon streams to jet products

ABSTRACT

A process of upgrading a heavy hydrocarbon feedstock comprising contacting a heavy hydrocarbon feedstock with a catalyst in the presence of hydrogen in a reactor system, containing the catalyst as the only catalyst, wherein the catalyst, is prepared by sulfiding a catalyst precursor obtained by mixing at reaction conditions, to form a precipitate or cogel, at least a Group VIII metal compound in solution; at least a Group VIB metal compound in solution; and, at least an organic oxygen containing ligand in solution, and thereby producing a fuel product.

FIELD OF THE INVENTION

The present invention relates to a hydroconversion process wherein ahydrocarbon feed comprising aromatic compounds is contacted withhydrogen in the presence of a catalyst composition which catalystcomposition comprises at least one Group VIII metal and at least oneGroup VIB metal Specifically, the present invention is directed to aprocess for converting heavy hydrocarbonaceous feeds to jet productsusing a single catalyst system.

BACKGROUND OF THE INVENTION

Heavy hydrocarbon streams, such as FCC-Light Cycle Oil (“LCO”), MediumCycle Oil (“MCO”), and Heavy Cycle Oil (“HCO”), have a relatively lowvalue. Typically, such hydrocarbon streams are upgraded throughhydroconversion including hydrotreating and/or hydrocracking.

Hydrotreating catalysts are well known in the art. Conventionalhydrotreating catalysts comprise at least one Group VIII metal componentand/or at least one Group VIB metal component either as a bulkunsupported catalyst or, more commonly, as a catalyst supported on arefractory oxide support. The Group VIII metal component is typicallybased on a non-noble metal, such as nickel (Ni) and/or cobalt (Co).Group VIB metal components include those based on molybdenum (Mo) andtungsten (W). The most commonly applied refractory oxide supportmaterials are inorganic oxides such as silica, alumina andsilica-alumina. Examples of conventional hydrotreating catalyst areNiMo/alumina, CoMo/alumina and NiW/silica-alumina. In some cases,platinum and/or palladium containing catalysts may be employed.

Hydrotreating catalysts are normally used in processes wherein ahydrocarbon feed is contacted with hydrogen to reduce its content ofaromatic compounds, sulfur compounds, and/or nitrogen compounds.Typically, hydrotreating processes wherein reduction of the aromaticscontent is the main purpose are referred to as hydrogenation orhydrofinishing processes, while processes predominantly focusing onreducing sulfur and/or nitrogen content are referred to ashydrodesulfurization and hydrodenitrogenation, respectively.Traditionally, the term “hydrotreating” is used to describehydrodesulfurization and hydrodenitrogenation while the term“hydrofinishing” is used to describe the hydrogenation of aromatics. Thepresent invention follows this tradition of terminologies. Typically,hydrocracking converts feed to lighter products such as naphtha or gasvia cracking and dealkylation as well as to low volumetric energydensity components via unselective ring opening. One disadvantage ofhydrocracking is that it leads to a higher H2 consumption due tocracking, dealkylation and unselective ring opening. The presentinvention avoids these disadvantages while producing jet products whichnot only meet the requirements of the jet specifications but alsopossess high volumetric energy density.

The present invention is directed to a method of upgrading heavyhydrocarbon feedstocks with an unsupported catalyst in a fixed bedreactor system. Specifically, the method of the present invention isdirected to a method of upgrading heavy hydrocarbon feedstocks to jetproducts with high volumetric energy density.

DESCRIPTION OF THE RELATED ART

Marmo, U.S. Pat. No. 4,162,961 discloses a cycle oil that ishydrogenated under conditions such that the product of the hydrogenationprocess can be fractionated.

Myers et al., U.S. Pat. No. 4,619,759 discloses the catalytichydrotreatment of a mixture comprising a resid and a light cycle oilthat is carried out in a multiple catalyst bed in which the portion ofthe catalyst bed with which the feedstock is first contacted contains acatalyst which comprises alumina, cobalt, and molybdenum and the secondportion of the catalyst bed through which the feedstock is passed afterpassing through the first portion contains a catalyst comprising aluminato which molybdenum and nickel have been added.

Kirker et al., U.S. Pat. No. 5,219,814 discloses a moderate, pressurehydrocracking process in which highly aromatic, substantiallydealkylated feedstock is processed to high octane, gasoline and lowsulfur distillate by hydrocracking over a catalyst, preferablycomprising ultrastable Y and Group VIII metal and a Group VI metal, inwhich the amount of the Group VIII metal content is incorporated atspecified proportion to the framework aluminum content of theultrastable Y component.

Kalnes, U.S. Pat. No. 7,005,057 discloses a catalytic hydrocrackingprocess for the production of ultra low sulfur diesel wherein ahydrocarbonaceous feedstock is hydrocracked at elevated temperature andpressure to obtain conversion to diesel boiling range hydrocarbons.

Barre et al., U.S. Pat. No. 6,444,865 discloses a catalyst, whichcomprises from 0.1 to 15 wt % of noble metal selected from one or moreof platinum, palladium, and iridium, from 2 to 40 wt % of manganeseand/or rhenium supported on an acidic carrier, used in a precess whereina hydrocarbon feedstock comprising aromatic compounds is contacted withthe catalyst at elevated temperature, in the presence hydrogen.

Barre et al., U.S. Pat. No. 5,868,921 discloses a hydrocarbondistillate, fraction that is hydrotreated, in a single stage by passingthe distillate fraction downwardly over a stacked bed of twohydrotreating catalysts.

Fujukawa et al., U.S. Pat. No. 6,821,412 discloses a catalyst forhydrotreatment of gas oil containing defined amounts of platinum,palladium and in support of an inorganic oxide containing a crystallinealumina having a crystallite diameter of 20 to 40 Å. Also disclosed is amethod, for hydrotreating gas oil containing an aromatic compound in thepresence of the above catalyst at defined conditions.

Kirker et al., U.S. Pat. No. 4,968,402 discloses a one stage process forproducing high octane gasoline from a highly aromatic hydrocarbonfeedstock.

Brown et al., U.S. Pat. No. 5,520,799 discloses a process for upgradingdistillate feeds. Hydroprocessing catalyst is placed in a reaction zone,which is usually a fixed bed reactor under reactive conditions and lowaromatic diesel and jet fuel are produced.

Soled et al., U.S. Pat. No. 6,162,350 discloses a slurry hydroprocessingprocess for upgrading hydrocarbon feedstock with a bulk mixed metalcatalyst preferentially comprised of Ni—Mo—W.

Haluska et al., U.S. Pat. No. 6,755,963 discloses a slurryhydroprocessing process for upgrading hydrocarbon resid feedstock with abulk mixed metal catalyst comprised of one or more Group VIII metals andone or more Group VIB metals.

Riley et al., U.S. Pat. No. 6,582,590 discloses a multistage slurryhydroprocessing process for upgrading hydrocarbon feedstock with a bulkmixed metal catalyst comprised of one or more Group VIII metals and atleast two Group VIB metals.

Riley et al., U.S. Pat. No. 7,229,548 discloses a slurry hydroprocessingprocess for upgrading a naphtha feedstock to a naphtha product with lessthan about 10 wppm of nitrogen and less than about 15 wppm sulfur usinga bulk mixed metal catalyst comprised of one or more Group VIII metalsand at least two Group VIB metals.

Riley et al., U.S. Pat. No. 6,929,738 discloses a two stage slurryhydroprocessing process for hydrodesulfurization of high sulfur (greaterthan about 3,000 ppm sulfur) distillates with a bulk mixed, metalcatalyst comprised of one or more Group VIII metals and at least twoGroup VIB metals.

Hou et al., U.S. Pat. No. 6,712,955 and Riley et al., U.S. Pat. No.6,783,663 discloses a slurry hydroprocessing process for upgradinghydrocarbon feedstock with a bulk mixed metal catalyst comprised of oneor more Group VIII metals and at least two Group VIB metals.

Demmin et al., U.S. Pat. No. 6,620,313 discloses a Ni—Mo—W catalyst usedin a multi step process to hydroprocess a raffinate feedstock.

SUMMARY OF THE INVENTION

In one embodiment of the invention, there is provided a process forupgrading hydrocarbon feedstocks, which process comprises contacting aheavy hydrocarbon feedstock with a catalyst in the presence of hydrogenin a reactor system, containing said catalysta as the only catalyst,wherein the catalyst, is prepared from a catalyst of the generalformula:

A_(v)[(M^(VIII))(OH)_(x)(X)_(y)]_(z) (M^(VIB)O₄) wherein

-   -   A is at least one of an alkali metal cation, an ammonium, an        organic ammonium and a phosphonium cation,    -   M^(VIII) is at least a Group VIII metal,    -   X is at least an organic oxygen-containing ligand,    -   M^(VIB) is at least a Group VIB metal,        -   and wherein M^(VIII):M^(VIB) has an atomic ratio of 100:1 to            1:100; and thereby producing a fuel product.

In one embodiment of the present invention, there is provided a processof upgrading a heavy hydrocarbon feedstock comprising contacting a heavyhydrocarbon feedstock with a catalyst in the presence of hydrogen in areactor system, at hydroprocessing conditions, containing said catalystas the only catalyst, wherein the catalyst, is prepared by sulfiding acatalyst precursor obtained by mixing at reaction conditions, to form aprecipitate or cogel, at least a Group VIII metal compound in solution;at least a Group VIB metal compound in solution; and, at least anorganic oxygen containing ligand in solution, and thereby producing afuel product.

The process according to the invention can achieve increased hydrocarbonproductivity through an increase in the conversion of lower valuehydrocarbon streams to higher quality products in a single reactorsystem.

The process of the invention is desirably practiced with a light cycleoil (LCO) feedstock and a catalyst comprising nickel, molybdenum, andtungsten to produce jet products.

DETAILED DESCRIPTION OF THE INVENTION

While the invention is susceptible to various modifications andalternative forms, specific embodiments thereof are herein described indetail. It should be understood, however, that the description herein ofspecific embodiments is not intended to limit the invention to theparticular forms disclosed, but on the contrary, the intention is tocover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention as defined by the appended claims.

DEFINITIONS

FCC—The term “FCC” refers to fluid catalytic crack-er, -ing, or -ed.

As used herein, the terms “feedstock” and “feedstream” areinterchangeable.

As used herein, “hydroprocessing” is meant any process that is carriedout in the presence of hydrogen. Including, but not limited to,hydrogenation, hydrofinishing, hydrotreating, hydrodesulphurization,hydrodenitrogenation, hydrodemetallation, hydrodearomatization,hydroisomerization, hydrodewaxing and hydrocracking including selectivehydro-ring-opening. Depending on the type of hydroprocessing and thereaction conditions, the products of hydroprocessing may show improvedviscosities, viscosity indices, saturates content, low temperatureproperties, volatilities and depolarization, etc.

Energy density—refers to the heat of combustion of a fuel, which isreleased during its combustion. The amount of heat released depends onwhether the water formed during combustion remains in the vapor phase oris condensed to a liquid. If the water is condensed to the liquid phase,it gives up its heat of vaporization in the process. In this case, thereleased heat is called gross heat of combustion. The net heat ofcombustion is lower than the gross heat of combustion because the waterremains in the gaseous-phase (water vapor). The net heat of combustionis the appropriate value for comparing fuels since engines exhaust wateras vapor. The net volumetric energy density describes the net energydensity of a fuel on the volumetric basis and is often given in Btu pergallon, for example, 125,000 Btu per gallon for a jet fuel and 130,000Btu per gallon for a diesel.

LHSV—refers to liquid hourly space velocity, which is the volumetricrate of the liquid feed (i.e., the volume of the liquid feed at 60° F.per hour) divided by the volume of the catalyst, and is given in hr⁻¹.

As used herein, “hydroprocessing” is meant any process that is carriedout in the presence of hydrogen, including, but not limited to,methanation, water gas shift reactions, hydrogenation, hydrotreating,hydrodesulphurization, hydrodenitrogenation, hydrodemetallation,hydrodearomatization, hydroisomerization, hydrodewaxing andhydrocracking including selective hydrocracking. Depending on the typeof hydroprocessing and the reaction conditions, the products ofhydroprocessing can show improved viscosities, viscosity indices,saturates content, low temperature properties, volatilities anddepolarization, etc.

As used herein, the term “catalyst precursor” refers to a compoundcontaining one or more Group VIII metals, one or more Group VIB metals,at least a hydroxide, and one or more organic oxygen-containing ligands,and which compound can be catalytically active after sulfidation as ahydroprocessing catalyst.

As used herein, the term “charge-neutral” refers to the fact that thecatalyst precursor carries no net positive or negative charge. The term“charge-neutral catalyst precursor” can sometimes be referred to simplyas “catalyst precursor.”

As used herein, the term “ammonium” refers to a cation with the chemicalformula NH₄ ⁺ or to organic nitrogen containing cations, such as organicquaternary amines.

As used herein, the term “phosphonium” refers to a cation with thechemical formula PH₄ ⁺ or to organic phosphorus-containing cations.

The term “Group VIII metal” refers to iron, cobalt, nickel, ruthenium,rhenium, palladium, osmium, iridium, platinum, and combinations thereofin their elemental, compound, or ionic form.

The term “Group VIB metal” refers to chromium, molybdenum, tungsten, andcombinations thereof in their elemental, compound, or ionic form.

The term oxoanion refers to monomeric oxoanions and polyoxometallates.

As used herein, the term “mixture” refers to a physical combination oftwo or more substances. The “mixture” can be homogeneous orheterogeneous and in any physical state or combination of physicalstates.

The term “reagent” refers to a raw material that can be used in themanufacture of the catalyst precursor of the invention. The term “metal”does not mean that the reagent is in the metallic form, but is presentas a metal compound.

As used herein the term “carboxylate” refers to any compound containinga carboxylate or carboxylic acid group in the deprotonated or protonatedstate.

As used herein the term “organic oxygen-containing ligand” refers to anycompound comprising at least one carbon atom, at least one-oxygen atom,and at least one hydrogen atom wherein said oxygen atom has one or moreelectron pairs available for co-ordination to the Group VIII or GroupVIB metal ion. In one embodiment, the oxygen atom is negatively chargedat the pH of the reaction. Examples of organic oxygen-containing ligandsinclude, but are not limited to, carboxylic acids, carboxylates,aldehydes, ketones, the enolate forms of aldehydes, the enolate forms ofketones, hemiacetals, and the oxo anions of hemiacetals.

The term “cogel” refers to a solid hydroxide co-precipitate of at leasttwo metals containing a water rich phase. “Cogelation” refers to theprocess of forming a cogel.

A. Overview

In one embodiment, the present invention is directed to a process ofupgrading heavy hydrocarbons comprising:

-   -   (a) Preparing a catalyst by sulfidation of a catalyst precursor        in which the catalyst precursor comprises at least one Group        VIII metal hydroxide, at least one Group VIB metal oxoanion, and        at least one oxygen containing coordinating ligand; and    -   (b) reacting a heavy hydrocarbon feedstream with the catalyst in        the presence of hydrogen in a fixed bed reactor;

B. Feed

Heavy hydrocarbon feedstock may be upgraded to a product having aboiling point range within jet boiling point ranges. The hydrocarbonfeedstock comprises FCC effluent, including FCC light, medium and heavycycle oil; fractions of jet and diesel fuels; coker product; coalliquefied oil; the product from the heavy oil thermal cracking process;the product from heavy oil hydrotreating and/or hydrocracking; straightrun cut from a crude unit; or mixtures thereof, and having a majorportion of the feedstock having a boiling range of from about 250° F. toabout 1200° F., and preferably from about 300° F. to about 1000° F. Theterm “major portion” as used in this specification and the appendedclaims, shall mean at least 50 wt %.

Typically, the feedstock may comprise at least 20 wt % ring-containinghydrocarbon compounds comprising aromatic moieties, naphthenic moietiesor both, up to 3 wt % sulfur and up to 1 wt % nitrogen. Preferably, thefeedstock may comprise at least 40 wt % ring-containing hydrocarboncompounds. More preferred, the feedstock may comprise at least 60 wt %ring-containing hydrocarbon compounds.

C. Catalyst

In one embodiment of the present invention, the catalyst employed isprepared from a catalyst precursor which may be sulfided therebyproducing an active catalyst which is used to produce the jet fuelproduct of the present invention.

Catalyst Precursor Formula: In one-embodiment, the charge-neutralcatalyst precursor composition is of the general formulaA_(v)[(M^(VIII))_(x)(OH)_(x)(X)_(y)]_(z) (M^(VIB)O₄), wherein A is oneor more monovalent cationic species, M^(VIII) is one or more Group VIIImetals, X is one or more organic ligand oxygen-containing ligands,M^(VIB) is one or more Group VIB metals with the atomic ratio ofM^(VIII):M^(VIB) between 100:1 and 1:100. In one embodiment, X isselected from the group of carboxylates, carboxylic acids, aldehydes,ketones, the enolate forms of aldehydes, the enolate forms of ketones,and hemiacetals, and combinations thereof. In one embodiment, A isselected from monovalent cations such as NH₄ ⁺, other quaternaryammonium ions, organic phosphonium cations, alkali metal cations, andcombinations thereof.

In one embodiment where both molybdenum and tungsten are used as the(M^(VIB)) Group VIB metals, the molybdenum to tungsten atomic ratio(Mo:W) is in the range of about 10:1 to 1:10. In another embodiment, theratio of Mo:W is between about 1:1 and 1:5. In an embodiment wheremolybdenum and tungsten are used as the Group VIB metals, thecharge-neutral catalyst precursor is of the formulaA_(v)[(M^(VIII))(OH)_(x)(X)_(y)]_(z)(Mo_(t)W_(t′)O₄). In yet anotherembodiment, where molybdenum and tungsten are used as the Group VIBmetals, chromium can be substituted for some or all of the tungsten withthe ratio of (Cr+W):Mo in the range of about 10:1 to 1:10. In anotherembodiment, the ratio of (Cr+W):Mo is between 1:1 and 1:5. In anembodiment where molybdenum, tungsten, and chromium are the Group VIBmetals, the charge-neutral catalyst precursor is of the formulaA_(v)[(M^(VIII))(OH)_(x)(X)_(y)]_(z) (Mo_(t)W_(t′)Cr_(t″)O₄).

In one embodiment where M^(VIII) is a mixture of two metals such as Niand Co, the charge-neutral catalyst precursor is of the formulaA_(v)[(Ni_(a)CO_(a′)Fe_(a″))(OH)_(x)(X)_(y)]_(z) (M^(VIB)O₄). In yetanother embodiment, M^(VIII) is a combination of three metals such asNi, Co and Fe, the charge-neutral catalyst precursor is of the formulaA_(v)[(Ni_(a)Co_(a′)Fe_(a″))(OH)_(x)(X)_(y)]_(z) (M^(VIB)O₄).

Group VIII Metal Component: In one embodiment, the Group VIII metal(M^(VIII)) compound is in a solution state, with the whole amount of theGroup VIII metal compound dissolved in a liquid to form a homogeneoussolution. In another embodiment, the Group VIII metal is partly presentas a solid and partly dissolved in the liquid. In a third embodiment, itis completely in the solid state.

The Group VIII metal compound can be a metal salt or mixture selectedfrom nitrates, hydrated nitrates, chlorides, hydrated chlorides,sulphates, hydrated sulphates, formates, acetates, hypophosphites, andmixtures thereof. In an embodiment, the Group VIII metal compound is anickel compound which is at least partly in the solid state, e.g., awater-insoluble nickel compound such as nickel carbonate, nickelhydroxide, nickel phosphate, nickel phosphite, nickel formate, nickelsulphide, nickel molybdate, nickel tungstate, nickel oxide, nickelalloys such as nickel-molybdenum alloys, Raney nickel, or mixturesthereof.

Group VIB Metal Component: The Group VIB metal (M^(VIB)) compound can beadded In the solid, partially dissolved, or solution state. In oneembodiment, the Group VIB metal compound is selected from molybdenum,chromium, tungsten components, and combinations thereof. Examples ofsuch compounds include, but are not limited to, alkali metal, alkalineearth, or ammonium metallates of molybdenum, tungsten, or chromium,(e.g., ammonium tungstate, meta-, para-, hexa-, or polytungstate,ammonium chromate, ammonium molybdate, iso-, peroxo-, di-, tri-, tetra-,hepta-, octa-, or tetradecamolybdate, alkali metal heptamolybdates,alkali metal orthomolybdates, or alkali metal isomolybdates), ammoniumsalts of phosphomolybdic acids, ammonium salts of phosphotunstic acids,ammonium salts of phosphochromic acids, molybdenum (di- and tri) oxide,tungsten (di- and tri) oxide, chromium or chromic oxide, molybdenumcarbide, molybdenum nitride, aluminum molybdate, molybdic-acid, chrormicacid, tungstic acid, Mo—P heteropolyanion compounds, Wo—Siheteropolyanion compounds, W—P heteropolyanion compounds. W—Siheteropolyanion compounds, Ni—Mo—W heteropolyanion compounds. Co—Mo—Wheteropolyanion compounds, or mixtures thereof, added in the solid,partially dissolved, or solute state.

Organic, Oxygen-Containing Ligands In one embodiment, the oxygencontaining ligand is a carboxylate containing compound. In oneembodiment, the carboxylate compound contains one or more carboxylatefunctional groups. In yet another embodiment, the carboxylate compoundcomprises monocarboxylates including, but not limited to, formate,acetate, propionate, butyrate, pentanoate, and hexanoate anddicarboxylates including, but not limited to, oxalate, malonate,succinate, glutarate, adipate, malate, maleate, or combinations thereof.In a fourth embodiment, the carboxylate compound comprises maleate.

The organic oxygen containing ligands can be mixed with the Group VIIImetal containing solution or mixture, the Group VIB metal containingsolution or mixture, or a combination of the Group VIII metal and GroupVIB metal containing precipitates, solutions, or mixtures. The organicoxygen containing ligands can be in a solution state, with the wholeamount of the organic oxygen containing ligands dissolved in a liquidsuch as water. The organic oxygen containing ligands can be partiallydissolved and partially in the solid state during mixing with the GroupVIII metal(s), Group VIB metal(s), or combinations thereof.

Methods for Making Hydroprocessing Catalyst Precursor: The preparationmethod allows systematic varying of the composition and structure of thecatalyst precursor by controlling the relative amounts of the elements,the types of the reagents, and the length and severity of the various,reactions and reaction steps.

The order of addition of the reagents used in forming the catalystprecursor may be in various ways. For example, organic oxygen containingligand can be combined with a mixture of Group VIII metals and Group VIBmetals prior to precipitation or cogelation. The organic oxygencontaining ligand can be mixed with a solution of a Group VIII metal,and then added to a solution of one or more Group VIB metals. Theorganic oxygen containing ligand can be mixed with a solution of one ormore Group VIB metals and added to a solution of one or more Group VIIImetals.

Forming a Precipitate or Cogel with Group VIB/Group VIII Metals: In oneembodiment of the process, the first step is a precipitation orcogelation step, which involves reacting in a mixture the Group VIIImetal component in solution and the Group VIB, metal component insolution to obtain a precipitate or cogel. The precipitation orcogelation is carried out at a temperature and pH which the Group VIIImetal compound and the Group VIB metal compound precipitate or form acogel. An organic oxygen containing ligand in solution or at leastpartially in solution is then combined with the precipitate or cogel toform an embodiment of the catalyst precursor.

In an embodiment, the temperature at which the catalyst precursor isformed is between 50-150° C. If the temperature is below the boilingpoint of the protic liquid, such as 100° C. in the case of water, theprocess is generally carried out at atmospheric pressure. Above thistemperature, the reaction is generally carried out at increasedpressure, such as in an autoclave. In one embodiment, the catalystprecursor is formed at a pressure of between about 0 to 3000 psig. In asecond embodiment, the catalyst precursor is formed at a pressure ofbetween about 100 to 1000 psig.

The pH of the mixture can be changed to increase or decrease the rate ofprecipitation or cogelation, depending on the desired characteristics ofthe product. In one embodiment, the mixture is kept at its natural pHduring the reaction step(s). In another embodiment, the pH is maintainedin the range of between about 0-12. In another embodiment, the pH ismaintained in the range of between about 4-10. In a further embodiment,the pH is maintained in the range of between about 7-10. Changing the pHcan be done by adding base or acid to the reaction mixture, or addingcompounds, which decompose upon temperature increase into hydroxide ionsor H⁺ ions that respectively increase or decrease the pH. Examplesinclude urea, nitrites, ammonium hydroxide, mineral acids, organicacids, mineral bases, and organic bases.

In one embodiment, the reaction of Group VIB and Group VIII metalcomponents is carried out with water-soluble nickel, molybdenum andtungsten metal salts. The solution can further comprise other Group VIIImetal components, e.g., cobalt or iron components such as Co(NO₃)₂ or(CH₃CO₂)₂Co, as well as other Group VIB metal components such aschromium components.

The reaction is carried with the appropriate metal salts resulting inprecipitate or cogel combinations of nickel/molybdenum/tungsten,cobalt/molybdenum/tungsten, nickel/molybdenum, nickel/tungsten,cobalt/molybdenum, cobalt/tungsten, ornickel/cobalt/molybdenum/tungsten. An organic oxygen containing ligandcan be added prior to or after precipitation or cogelation of the GroupVIII and/or Group-VIB metal components.

The metal precursors can be added to the reaction mixture in solution,suspension or a combination thereof. If soluble salts are added as such,they will dissolve in the reaction mixture and subsequently beprecipitated or cogeled. The solution can be heated optionally undervacuum to effect precipitation and evaporation of the water.

After precipitation or cogelation, the catalyst precursor can be driedto remove water. Drying can be performed under atmospheric conditions orunder an inert atmosphere such as nitrogen, argon, or vacuum. Drying canbe effected at a temperature sufficient to remove water but not removalof organic components. Preferably drying is performed at about 120° C.until a constant weight of the catalyst precursor is reached.

Characterization of the Catalyst Precursor: Characterization of thecharge-neutral catalyst precursor of the formulaA_(v)[(M^(VIII))(OH)_(x)(X)_(y)]_(z)(M^(VIB)O₄), can be performed usingtechniques known in the art, including, but not limited to, powder x-raydiffraction (PXRD), elemental analysis, surface area measurements,average pore size distribution, average pore volume. Porosity andsurface area measurements can be performed using BJH analysis underB.E.T. nitrogen adsorption conditions.

In one embodiment, the catalyst precursor has an average pore volume of0.05-5 ml/g as determined by nitrogen adsorption. In another embodiment,the average pore volume is 0.14 ml/g. In a third embodiment, the averagepore volume is 0.1-3 ml/g.

In one embodiment, the catalyst precursor has a surface area of at least10 m²/g. In a second embodiment, the catalyst precursor has a surfacearea of at least 50 m²/g. In a third embodiment, the catalyst precursorhas a surface area of at least 150 m²/g.

In one embodiment, the catalyst precursor has an average pore size, asdefined by nitrogen adsorption, of 2-50 nanometers. In a secondembodiment, the catalyst precursor has an average pore size, as definedby nitrogen adsorption, of 3-30 nanometers. In a third embodiment, thecatalyst precursor has an average pore size, as defined by nitrogenadsorption, of 4-15 nanometers.

Shaping Process In one embodiment, the catalyst precursor compositioncan generally be directly formed into various shapes depending on theintended commercial use. These shapes can be made by any suitabletechnique, such as by extrusion, pelletizing, beading, or spray drying.If the amount of liquid of the bulk catalyst precursor composition is sohigh that it cannot be directly subjected to a shaping step, asolid-liquid separation can be performed before shaping.

Addition of Pore forming Agents The catalyst precursor can be mixed witha pore forming agent including, but not limited to steric acid,polyethylene glycol polymers, carbohydrate polymers, methacrylates, andcellulose polymers.

For example, the dried catalyst precursor can be mixed with cellulosecontaining materials such as methylcellulose, hydroxypropylcellulose, orother cellulose ethers in a ratio of between 100:1 and 10:1 (wt. %catalyst precursor to wt. % cellulose) and water added until a mixtureof extrudable consistency is obtained. Examples of commerciallyavailable cellulose based pore forming agents include but are notlimited to: methocel (available from bow Chemical Company), avicel(available from FMC Biopolymer), and, porocel (available from Porocel).The extrudable mixture: can be extruded and then optionally dried. Inone embodiment, the drying can be performed under an inert atmospheresuch as nitrogen, argon, or vacuum. In another embodiment, the dryingcan be performed at elevated temperatures between 70 and 200° C. In yetanother embodiment, the drying is performed at 120° C.

Optional Component—Diluent: In one embodiment a diluent is optionallyincluded in the process for making the catalyst. Generally, the diluentmaterial to be added has less catalytic activity than the catalystprepared from the catalyst precursor composition (without the diluent)or no catalytic activity at all. Consequently, by adding a diluent, theactivity of the catalyst can be reduced. Therefore, the amount ofdiluent to be added in the process of the invention generally depends onthe desired activity of the final catalyst composition. Diluent amountsfrom 0-95 wt. % of the total composition can be suitable, depending onthe envisaged catalytic application.

The diluent can be added to the Group VIII metal or metal containingmixtures or the Group VIB metal or metal containing mixtures eithersimultaneously or one after the other. Alternatively, the Group VIII andGroup VIB metal mixtures can be combined together and subsequently adiluent can be added to the combined metal mixtures. It is also possibleto combine part of the metal mixtures either simultaneously or one afterthe other, to subsequently add the diluent and to finally add the restof the metal mixtures either simultaneously or one after the other.Furthermore, it is also possible to combine the diluent with metalmixture's in the solute state and to subsequently add a metal compoundat least partly in the solid state. The organic oxygen containing ligandis present in at least one of the metal containing mixtures.

In one embodiment, the diluent is composited with a Group VIB metaland/or a Group VIII metal, prior to being composited with the bulkcatalyst precursor composition and/or prior to being added during thepreparation thereof. Compositing the diluent with any of these metals inone embodiment is carried out by impregnation of the solid diluent withthese materials.

Optional diluent materials include any materials that are conventionallyapplied as a diluent or binder in hydroprocessing catalyst precursors.Examples include silica, silica-alumina, such as conventionalsilica-alumina, silica-coated alumina and alumina-coated silica, aluminasuch as (pseudo)boehmite, or gibbsite, titania, zirconia, cationic claysor anionic clays such as saponite, bentonite, kaoline, sepiolite orhydrotalcite, or mixtures thereof. In one embodiment, binder materialsare selected from silica, colloidal silica doped with aluminum,silica-alumina, alumina, titanic, zirconia, or mixtures thereof.

These diluents can be applied as such or after peptization. It is alsopossible to apply precursors of these diluents that, during the process,are converted into any of the above-described diluents. Suitableprecursors are, e.g., alkali metal aluminates (to obtain an aluminadiluent), water glass (to obtain a silica diluent), a mixture of alkalimetal aluminates and water glass (to obtain a silica alumina diluent), amixture of sources of a di-, tri-, and/or tetravalent metal such as amixture of water-soluble salts of magnesium, aluminum and/or silicon (toprepare a cationic clay and/or anionic clay), chlorohydrol, aluminumsulfate, or mixtures thereof.

Other Optional Components: If desired, other materials, including othermetals can be added in addition to the components described above. Thesematerials include any material that is added during conventionalhydroprocessing catalyst precursor preparation. Suitable examples arephosphorus compounds, borium compounds, additional transition metals,rare earth metals, fillers, or mixtures thereof. Suitable phosphoruscompounds include ammonium phosphate, phosphoric acid, or organicphosphorus compounds. Phosphorus compounds can be added at any stage ofthe process steps. Suitable additional transition metals that can beadded to the process steps include are, e.g., rhenium, ruthenium,rhodium, iridium, chromium, vanadium, iron, cobalt, platinum, palladium,and cobalt. In one embodiment, the additional metals are applied in theform of water-insoluble compounds. In another embodiment, the additionalmetals are added in the form of water soluble compounds. Apart fromadding these metals during the process, it is also possible to compositethe final catalyst precursor composition therewith the optionalmaterials. It is, e.g., possible to impregnate the final catalystprecursor composition with an impregnation solution comprising any ofthese, additional materials.

Sulfiding Agent Component: The charge-neutral catalyst precursor of thegeneral formula A_(v)[(M^(VIII))(OH)_(x)(X)_(y)]_(z)(M^(VIB)O₄) can besulfided to form an active catalyst. In one embodiment, the sulfidingagent is in the form of a solution, which, under prevailing conditions,is decomposable into hydrogen sulphide. In one embodiment, the sulfidingagent is present in an amount in excess of the stoichiometric amountrequired to form the sulfided catalyst from the catalyst precursor. Inanother embodiment, the amount of sulfiding agent represents a sulphurto Group VIB metal mole ratio of at least 3 to 1 to produce a sulfidedcatalyst from the catalyst precursor.

In one embodiment, the sulfiding agent is selected from the group ofammonium sulfide, ammonium polysulfide ([(NH₄)₂S_(x)), ammoniumthiosulfate ((NH₄)₂S₂O₃), thiosulfate Na₂S₂O₃), thiourea CSN₂H₄, carbondisulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS),tertiarybutyl polysulfide (PSTB) and tertiarynonyl polysulfide (PSTN),and the like. In another embodiment, the sulfiding agent is selectedfrom alkali- and/or alkaline earth metal sulfides, alkali- and/oralkaline earth metal hydrogen sulfides, and mixtures thereof. The use ofsulfiding agents containing alkali- and/or alkaline earth metals canrequire an additional separation process step to remove the alkali-and/or alkaline earth metals from the spent catalyst.

In one embodiment, the sulfiding agent is ammonium sulfide in aqueoussolution, which aqueous ammonium sulfide solution can be synthesizedfrom hydrogen sulfide and ammonia refinery off-gases. This synthesizedammonium sulfide is readily soluble in water and can easily be stored inaqueous solution in tanks prior to use. Since the ammonium sulfidesolution is denser than reside, it can be separated easily in a settlertank after reaction.

The sulfiding agent can be elemental sulfur mixed with the catalystprecursor during or prior to extrusion. The elemental sulfur can beco-extruded with the catalyst precursor to form active catalyst in situduring hydrotreatment.

In one embodiment, hydrocarbon feedstock is used as a sulfur source forperforming the sulfidation of the catalyst precursor. Sulfidation of thecatalyst precursor by a hydrocarbon feedstock can be performed in one ormore hydrotreating reactors during hydrotreatment.

Sulfiding Step: Sulfiding of the catalyst precursor to form the catalystcan be performed prior to introduction of the catalyst into thehydrotreating reactor, or in situ in the reactor. In one embodiment, thecatalyst precursor is converted into an active catalyst upon contactwith the sulfiding agent at a temperature ranging from 70° C. to 500°C., from 10 minutes to 5 days, and under a H₂-containing gas pressure.If the sulfidation temperature is below the boiling point of thesulfiding agent, such as 60-70° C. in the case of ammonium sulfidesolution, the process is generally carried out at atmospheric pressure.Above the boiling temperature of the sulfiding agent/optionalcomponents, the reaction is generally carried out at an increasedpressure, such as in an autoclave.

In one embodiment, the sulfidation is carried out at a temperatureranging from room temperature to 400° C. and for ½ hr. to 24 hours. Inanother embodiment, the sulfidation is at 150° C. to 300° C. In yetanother embodiment, the sulfidation is between 300-400° C. underpressure. In a fourth embodiment, the sulfidation is with an aqueousammonium sulfide solution at a temperature between 0 and 50° C., and inthe presence of at least a sulfur additive selected from the group ofthiodazoles, thio acids, thio amides, thiocyanates, thio esters, thiophenols, thiosemicarbazides, thioureas, mercapto alcohols, and mixturesthereof.

In one embodiment of the present invention, the catalyst of the presentinvention optionally can include an additional structural supportmaterial such as a refractory metal oxide material such as for examplesilica, alumina, magnesia, titania, etc. and mixtures thereof. Thestructural support can be in any form including for example monolith,spheres, or hollow cylinders. More specifically the metal oxide materialcan include “supports” such as alumina, silica, silica-alumina,silicate, alumino-silicate, magnesia, zeolite, active carbon, titaniumoxide, thorium oxide, clay and any combination of these supports. In oneembodiment of the present invention preferably, the invention's catalystcan contain between 50% and 95% by weight of structural support. In oneembodiment of the present invention, the preferred support was zirconia.

D. Process Conditions and Equipment

In one embodiment, the heavy hydrocarbon feedstream is reacted with thecatalyst in the presence of hydrogen in a fixed bed reactor system. Thefixed bed reactor system-comprises at least one reactor. Additionally,more than one reactor may be employed in either series or parallel orboth. Each reactor employed uses the catalyst described herein. Byoptimizing the Group VIII and Group VIB metal components and ratios,these catalysts used in the process of this invention can be located ina single reactor to convert LCO in one reactor directly to jet products.

The reaction zone comprises the catalyst in a fixed bed. The heavyhydrocarbon feedstream is fed to the reaction zone, which has atemperature of from about 300° F. to about 900° F., thereby producing areaction product. In a preferred embodiment the feedstream is LCO andthe reaction products are jet fuel products.

Typically, the contacting of the hydrocarbon feedstock takes place inthe reactor wherein the feedstock is contacted with the catalyst. Thereaction occurs at pressures ranging from 100 psig to 3000 psig,hydrocarbon feed LHSV (Liquid Hourly Space Velocity) ranging from 0.1 to10 hr⁻¹, and a ratio of hydrogen to hydrocarbon ranging from about400-20,000 SCF/bbl. If a higher conversion of the hydrocarbon feedstockis desirable, then the process optionally includes a separation stagefor recovering at least a portion of the product which may containunconverted feedstock. At least a portion of the product stream is then,optionally, recycled to the reactor system. In case the catalyst isdeactivated by coke deposit or other poisons, the catalyst activity canbe rejuvenated via regeneration. Processes which are suitable forregeneration are known to those skilled in the art.

Treating the hydrocarbon feed at the above conditions can substantiallyremove most of the sulfur and nitrogen compounds as well as partiallyhydrogenate the aromatic compounds to give a final aromatics contentbelow 25% providing hydrocarbon products that are low in sulfur andnitrogen and within jet fuel specifications. More specifically, theinventive method can reduce the amount of sulfur to less than about 15wppm, more preferably less than about 10 wppm and most preferably lessthan about 5 wppm. It also can reduce the amount of nitrogen to lessthan about 10 wppm, more preferably to less than about 5 wppm and mostpreferably less than about 1 wppm.

E. Product

The method employed in the present invention upgrades heavy hydrocarbonfeedstocks to jet fuel products. It has been discovered that the presentmethod employed produces jet fuel products that have a net heat ofcombustion of greater than at least 125,000 Btu/gal, preferably the netheat of combustion is greater than at least 127,000 Btu/gal, morepreferably 128,500 Btu/gal, even more preferably 129,500 Btu/gal.Furthermore, the product meets the specifications for jet fuel.Specifically, the product has a freezing point below 40° C. for jetfuel. The product has a smoke point greater than 18 mm. The product hasa viscosity of less than 8 cSt at −20 degrees Celsius. The product has adensity of less than 0.840 g/cc at −20 degrees Celsius.

Other embodiments will be obvious to those skilled in the art.

EXAMPLES

The following examples are presented to illustrate specific embodimentsof this invention and are not to be construed in any way as limiting thescope of the invention.

Example 1 Catalyst Precursor Formation

A catalyst precursor of the formula (NH₄)⁺{[Ni_(2.6)(OH)_(2.08)(C₄H₂O₄²⁻)_(0.06)] (MO_(0.35)W_(0.65)O₄)₂} was prepared as follows: 52.96 g ofammonium heptamolybdate (NH₄)₆Mo₇O₂₄.4H₂O was dissolved in 2.4 L ofdeionized (DI) water at room temperature. The pH of the resultingsolution was within the range of 5-6. 73.98 g of ammonium metatungstatepowder was then added to the above solution and stirred at roomtemperature until completely dissolved. 90 ml of concentrated (NH₄)OHwas added to the solution with constant stirring. The resultingmolybdate/tungstate solution, was stirred for 10 minutes and the pHmonitored. The solution had a pH in the range of 9-10. A second solutionwas prepared containing 174.65 g of Ni(NO₃)₂6H₂O dissolved in 150 ml ofdeionized water and heated to 90° C., thereby producing a hot nickelsolution which was then slowly-added over 1 hr to themolybdate/tungstate solution. The resulting mixture was heated to 91° C.and stirred for another 30 minutes. The pH of the solution was in therange of 5-6. A blue-green precipitate formed and the precipitate wascollected by filtration. The precipitate was dispersed into a solutionof 10.54 g of maleic acid dissolved in 1.8 L of DI water and heated to70° C. The resulting slurry was stirred for 30 min. at 70° C., filteredto produce a precipitate which was collected and vacuum dried at roomtemperature overnight. The material was then further dried at 120° C.for 12 hr. The resulting material has a typical XRD pattern with a broadpeak at 2.5 Å, denoting an amorphous Ni—OH containing material. Surfacearea measurements were within the range of 50-150 m²/g and an averagepore volume within the range of 0.1-0.2 cc/g with an average pore sizeof 5-50 nm as measured by BET method.

Example 2 Sulfidation

6.5 cc of the catalyst precursor of Example 1 was placed in a tubularreactor and first purged with 700 cc/min N2 at 100° F. overnight. Thenthe temperature was increased to 450° F. in 4 hours. After having beenheld at 450° F. in this N₂ flow for 1 hour, it was switched to 700cc/min H₂ and the pressure was increased to 800 psig. It's held at 450°F. and 800 psig in 700 cc/min H₂ for 1 hour. Then the sulfiding feedcontaining 6 wt. % DMDS (dimethyl disulfide) in n-heptane was introducedat 36 cc/hr at 800 psig, 450° F. and 700 cc/min H₂ and it was held for 2hours under these conditions. Subsequently the temperature was increasedfrom 450° F. to 650° F. in 4 hours and it was held at 650° F. for 2hours. With the sulfiding feed still on, the temperature was droppedfrom 650° F. to ˜300° F. as soon as possible. Then the sulfiding feedwas stopped, the pressure was increased to the pre-selected reactionpressure such as 1000 psig and the H₂ rate was adjusted to 77.2 cc/min.At this stage, the FCC LCO was started with a rate of 6.5 cc/hr at a H₂rate of 77.2 cc/min, 1000 psig and ˜300° F. Subsequently the reactortemperature was increased from ˜300° F. to a pre-selected reactiontemperature such as 600° F. at a rate of 1° F./min. Then the reactionproceeded at 6.5 cc/hr feed, 77.2 cc/min H₂, 600° F. and 1000 psig.

Example 3 Catalysts

The following catalysts were used in the example of the invention or inthe comparative examples.

(1) The catalyst of the invention is hereinafter referred to as Ni—Mo—W,which was prepared according to Examples 1 and 2.(2) A hydrotreating catalyst comprising molybdenum and nickel supportedon an alumina base is hereinafter referred to as Ni—Mo.(3) A hydrofinishing catalyst comprising platinum and palladiumsupported on a mixed silica-alumina/alumina base is hereinafter referredto as Pt—Pd.

Example 4 Feedstock

Table 1 discloses the properties of the feedstock used in the presentinvention. The feedstock is a light cycle oil (LCO) product from theFluid Catalytic Cracking unit in a refinery. The feedstock was: alsoanalyzed with simulated distillation. The results of the simulateddistillation are listed in Table 2. This feedstock has not beenhydrotreated.

Example 5 Upgrade of LCO to Jet Fuels with Ni—Mo—W Catalyst of thePresent Invention as a Single Catalyst in a Single Fixed Bed Reactor

The FCC LCO feed, as described in Table 1 and Table 2 in Example 4, washydroprocessed in a single fixed bed reactor at a feed rate of 6.5 cc/hrover 6.5 cc of the Ni—Mo—W catalyst of the present invention, asdescribed in Example, 3′. The reactor temperature was 600° F. and thereactor pressure was 1000 psig. Hydrogen feed rate was 77.2 cc/min.

The catalytic results are also listed in Table 1. The results from thesimulated distillation are also listed in Table 2. The results indicatethat the jet specifications are met.

Comparative Example 1 Upgrade of LCO to Jet Fuels with Ni—Mo Catalyst asa Single Catalyst in one Single Fixed Bed Reactor

The FCC LCO feed, as described in Table 1 and Table 2 in Example 4, washydrotreated in a fixed bed reactor at a feed rate of 11.2 cc/hr over5.9 g of the Ni—Mo catalyst described in Example 3 to compare withNi—Mo—W catalyst of the invention described in Example 5. In thiscomparative example, the temperature was 660° F. and the pressure was1700 psig. Hydrogen rate was 300 cc/min.

The catalytic results are also listed in Table 1. The results from thesimulated distillation are also listed in Table 2. The results indicatethat the jet product prepared with such a Ni—Mo catalyst does not meetthe jet specifications and demonstrate the advance of Ni—Mo—W catalystof the prevent invention described in Example 5, especially due to itshigh activity at a low pressure of 1000 psig and a low temperature of600° F.

Comparative Example 2 Upgrade of LCO to Jet Fuels with Ni—MoHydrotreating and Pt—Pd Hydrofinishing catalysts: in Two Fixed BedReactors

In Comparative Example 1, the FCC LCO feed described in Table 1 andTable 2 in Example 4 was hydrotreated in a fixed bed reactor at a feedrate of 11.2 cc/hr over 5.9 g of the Ni—Mo catalyst described in Example3. The resulting hydrotreating product produced in this first reactorwas then hydrofinished in a second fixed bed reactor at a feed rate of 4cc/hr over 4.7 g of platinum/palladium hydrofinishing catalyst describedin Example 3. The temperature of this second reactor containing Pt/Pdcatalyst was 550° F. and the pressure was 1000 psig. Hydrogen rate was100 cc/min. Thus, a jet product is produced via a two-stagehydrotreating-hydrofinishing reactor system with each stage containingone catalyst.

The properties of the jet product produced from this two stage reactorsystem containing two catalysts are also listed in Table 1. The reactionproduct was also analyzed with simulated distillation. The results ofthe simulated distillation are also listed in Table 2.

The results show the improvement of jet fuel properties using such atwo-stage hydroprocess which combines Ni—Mo and Pt/Pd catalysts, asdemonstrated, for example, by the improved smoke point with still a highnet heat of combustion of 128,781 Btu/gallon. By comparison to Example 5which employs only a single Ni—Mo—W catalyst in a single reactor, theprocess of Comparative Example 2 is undesirable because a hydrotreatingcatalyst is used in one reactor and a hydrofinishing catalyst is used inanother reactor to produce a high energy density jet fuel product. Itmay be economically disadvantageous to use more than one catalyst andmore than one reactor to upgrade LCO to a high energy density jet fuelproduct.

TABLE 1 Properties of FCC LCO Feedstock of Example 4 and Jet FuelsProduced in Example 5 as well as in Comparative Examples 1 and 2 JetProduct Produced Produced over Feed Produced over Ni—Mo and Untreatedover Ni—Mo Pt—Pd FCC LCO Ni—Mo—W Comparative Comparative Properties JetSpecs Example 4 Example 5 Example 1 Example 2 Density at 20° C.0.775-0.840 0.923 0.840 0.886 0.837 g/cc Smoke Point >18 5 24 8 25 mmFlash Point >38 85 67 80 64 ° C. Freezing Point <−40 −22.1 −61.1 −58.7−62.6 ° C. Viscosity at −20° C. <8 26.04 6.65 7.01 6.44 cSt Net Heat of137,034 129,965 132,700 128,781 Combustion Btu/gal Sulfur Content 22801.9 0.8 0.1 ppm wt. Nitrogen Content 232 <0.1 <0.1 <0.1 ppm wt.

TABLE 2 Simulated Distillation of FCC LCO Feedstock of Example 4 and JetFuels Produced in Example 5 as well as in Comparative Examples 1 and 2Temperature ° F. Jet Product Feed Produced over Produced over UntreatedProduced over Ni—Mo Ni—Mo and Pt—Pd Vol. FCC LCO Ni—Mo—W ComparativeComparative % Example 4 Example 5 Example 1 Example 2 0.5 289 244 287252 5 392 336 368 337 10 408 365 390 364 20 436 387 408 387 30 447 394422 391 40 451 402 436 396 50 455 409 442 406 60 458 420 450 416 70 473433 460 429 80 486 452 471 448 90 496 475 488 473 95 516 492 504 491 99547 532 540 534 99.5 562 545 552 549

1. A process of upgrading a heavy hydrocarbon feedstock comprising:contacting a heavy hydrocarbon feedstock with a catalyst in the presenceof hydrogen in a reactor system, containing said catalysta as the onlycatalyst, wherein the catalyst, is prepared from a catalyst of thegeneral formula:A_(v)[(M^(VIII))(OH)_(x)(X)_(y)]_(z) (M^(VIB)O₄) wherein A is at leastone of an alkali metal cation, an ammonium, an organic ammonium and aphosphonium cation, M^(VIII) is at least a Group VIII metal, X is atleast an organic oxygen-containing ligand, M^(VIB) is at least a GroupVIB metal, and wherein M^(VIII):M^(VIB) has an atomic ratio of 100:1 to1:100; and thereby producing a fuel product.
 2. The process of claim 1wherein the heavy hydrocarbon feedstock comprises, FCC effluent,including FCC light, medium and heavy cycle oil; fractions of jet anddiesel fuels; coker product; coal liquefied oil; the product from theheavy oil thermal cracking process; the product from heavy oilhydrocracking; straight run cut from a crude unit; or mixtures thereof.3. The process of claim 1 wherein the fuel product has a net heat ofcombustion of greater than 125,000 Btu/gal.
 4. The process of claim 1wherein the catalyst is unsupported.
 5. The process of claim 1 whereinthe catalyst is supported.
 6. The process of claim 1 wherein thefreezing point of the fuel product is below −40 degrees Celsius.
 7. Theprocess of claim 1 wherein the smoke point of the fuel product isgreater than 18 mm.
 8. The process of claim 1 wherein the flash point ofthe fuel product is greater than 38 degrees Celsius.
 9. The process ofclaim 1 wherein the density of the fuel product at 20 degrees Celsius isequal to or below 0.840 g/cc.
 10. The process of claim 1 wherein theviscosity of the fuel product at −20 degrees Celsius is below 8 cSt. 11.The process of claim 1 wherein the fuel product is a jet fuel product.12. A process of upgrading a heavy hydrocarbon feedstock comprisingcontacting a heavy hydrocarbon feedstock with a catalyst in the presenceof hydrogen in a reactor system, at hydroprocessing conditions,containing said catalyst as the only catalyst, wherein the catalyst, isprepared by sulfiding a catalyst precursor obtained by mixing atreaction conditions, to form a precipitate or cogel, at least a GroupVIII metal compound in solution; at least a Group VIB metal compound insolution; and, at least an organic oxygen containing ligand in solution,and thereby producing a fuel product.
 13. The process of claim 12wherein the heavy hydrocarbon feedstock comprises FCC effluent,including FCC light, medium and heavy cycle oil; fractions of jet anddiesel fuels; coker product; coal liquefied oil; the product from theheavy oil thermal cracking process; the product from heavy oilhydrocracking; straight run cut from a crude unit; or mixtures thereof.14. The process of claim 12 wherein the fuel product has a net heat ofcombustion of greater than 125,000 Btu/gal.
 15. The process of claim 12wherein the catalyst is unsupported.
 16. The process of claim 12 whereinthe catalyst is supported.
 17. The process of claim 12 wherein thefreezing point of the fuel product is below −40 degrees Celsius.
 18. Theprocess of claim 12 wherein the smoke point of the fuel product isgreater than 8 mm.
 19. The process of claim 12 wherein the flash pointof the fuel product is greater than 38 degrees Celsius.
 20. The processof claim 12 wherein the density of the fuel product at 20 degreesCelsius is equal to or below 0.840 g/cc.
 21. The process of claim 12wherein the fuel product is a jet fuel product.
 22. A product preparedby the process of, claim
 1. 23. A product prepared by the process ofclaim
 12. 24. The process of claim 1 wherein the feedstock comprises atleast 20 wt. % ring-containing hydrocarbon compounds comprising aromaticmoieties, naphthenic moieties or both.
 25. The process of claim 4wherein the feedstock comprises at least 20 wt % ring-containinghydrocarbon compounds comprising aromatic moieties, naphthenic moietiesor both.